Hair dyeing compositions

ABSTRACT

COMPOUNDS OF THE FOLLOWING FORMULAE WHICH ARE USEFUL IN HAIR DYEING COMPOSITIONS ARE DISCLOSED:   (4-NH2,2-(O2N-)PHENYL)-NH-(CH2)N-O-R1, (2-(O2N-),4-(R3-   N(-R2)-)PHENYL)-NH-(CH2)N-O-R1, AND (4-(O2N-),2-NH2-   PHENYL)-NH-(CH2)N-O-R1   WHEREIN N IS A WHOLE NUMBER OF 1 TO 4, R1 IS ALKYL OF 1 TO 8 CARBON ATOMS AND R2 AND R3 ARE HYDROXYALKYL OF UP TO 8 CARBON ATOMS.

United States Patent U.S. Cl. 260573 Claims ABSTRACT OF THE DISCLOSURECompounds of the following formulae which are useful in hair dyeingcompositions are disclosed:

N02 N01 NH! and I l-Ra 2 wherein n is a whole number of 1 to 4, R isalkyl of 1 to 8 carbon atoms and R and R are hydroxyalkyl of up to 8carbon atoms.

This is a division of application Ser. No. 458,443, filed May 24, 1965.

This invention relates to a novel group of alkyl derivatives ofnitroaminobenzenes that are particularly suitable as dye intermediatesor for dyeing keratinaceous materials. More particularly, it relates tosaid derivatives and compositions containing the same which may be usedto dye living human hair on the head or as dye intermediates inpreparing such dyes.

A variety of nitrophenylenediamine derivatives have been suggested foruse in the prior art as hair dyes. These, however, have been found inpractice to offer many disadvantages. Nitrophenylene-diamine dyes havingno substituents on the amino nitrogens have only a yellow or orangeshade. This is a disadvantage, since it is the red, blue and violetshades that are necessary for blending colors to arrive at naturallooking shades.

The simple alkyl-substituted nitrophenylenediamine derivatives whereinonly the simple alkyl substituents (e.g., methyl, ethyl) are on one orboth amino nitrogens are insufiiciently soluble or dispersible in water.Moreover, some dyes of this class tend to sublime readily when exposedto heat (e.g., body heat or sunlight). The dyeings with these dyes,thus, become weaker and off-shade on wearing.

It has also been suggested to employ, as hair dyes, compounds of thetype discussed above which have ionizable substituents on the alkylgroup bonded to the amino nitrogen. Substituted alkyl groups of thistype include --(CH ),,SO H and -CH CH NR +Cl However, dyes having the CHCOOH or (CH SO H groups have generally low afiinity to hair under themild conditions required. Dyes having the CH CH NR +CI group may havegood afiinity for hair but tend to dye unlevel, to be rubbed off readilyand to stain the skin.

-It has further been suggested to introduce such side chains as CH CHOH, -CH CH O-CH CH OH, and CH CH NH and CH CONH into thenitrophenylenediamine dyes as a chief group determining thecharacteristics of the dye. These groups tend to unduly raise thehydrophilic character of the dye when too many of them are present,resulting in poor dyeing. This is due to the fact that the dye wouldtend to stay in the dye bath 3,743,678 Patented July 3, 1973 rather thango onto the hair. Moreover, dyes having the aminoalkyl radical are highin basicity which makes the dye more soluble in acid media and lesslikely to go onto the haid from such media.

It has now been found that the disadvantages of the prior art dyes notedabove are avoided through the use of an alkyl derivative ofnitrophenylenediamines, defined in more detail below. Moreover, it hasalso been found that these may be readily prepared from certain alkylderivatives of nitroaminobenzenes, also defined below.

It is accordingly an object of the present invention to provide a groupof novel compounds that are suitable for use in dyeing keratinaceousmaterial, and particularly human hair.

It is another object of the present invention to provide a dyeintermediate suitable for synthesizing a dye that may be employed indyeing keratinaceous material, and particularly human hair.

It is a further object of the present invention to provide a compositionsuitable for dyeing keratinaceous material, and particularly livinghuman hair, which incorporates therein one or more of said novelcompounds.

It is still a further object of the present invention to provide amethod for dyeing keratinaceous materials, and particularly living humanhair which utilizes said composition mentioned in the above objects.

It is still another object of the present invention to provide novelalkyl derivatives of nitrophenylenediamines which avoid thedisadvantages of similar type compounds known in the prior art andmentioned above when used in dyeing human hair.

Other and more detailed objects will be apparent from the followingdescription and claims.

The above objects of the present invention are obtained by means ofcompounds of the following formula and particularly hair substantivedyes of this formula:

(I) N BB1 -S O NH-alkyI, S ogNH-hydroxyalkyl, S o N-alkyl,

alkyl S O N-alkyl, S 0 N-hydroryalkyl,

hydroxyalkyl hydroxyalkyl and S0:-alkyl the alkyl and hydroxyalkylportions of these groups containing l to 6 carbon atoms, and preferably1 to 3 carbon atoms.

In the compounds of Formula I in which both Y and Z are -N0 the abovedefinition provides that R is -alkylene-X. Although these have some useas dyes, they are principally useful as intermediates in preparing alkylderivatives of nitrophenylenediamines. On the other hand, compounds ofFormula I which are especially suitable as dyes are those compounds inwhich one of Y and Z is --NO and the other is NR R wherein R and R havethe same significance ascribed to them above.

When R R or R in Formula I above is an alkyl radical, it may be of anycarbon-chain length and may be either straight chain or branched chain.As a practical matter, however, the alkyl radical will rarely exceed 8carbon atoms. In the preferred form of the invention, the alkyl radicalsare lower alkyl radicals, and particularly alkyl radicals having from 1to 4 carbon atoms. By way of example, the following specific alkylradicals may be mentioned: methyl, ethyl, propyl, isopropyl, n-butyl,sec.- butyl, tert.-butyl, n-amyl, n-hexyl, and Z-ethylhexyl.

Similarly, when R R or R of Formula I are hydroxyalkyl radicals, thealkyl moiety of these radicals may be of any carbon-chain length andlikewise may be either straight chain or branched chain. Again, however,as a practical matter, they will rarely exceed 8 carbon atoms, andpreferably they will be lower alkyl groups containing from 1 to 4 carbonatoms.

Moreover, the number of hydroxy groups that will be contained in saidhydroxyalkyl radicals will also vary. For the most part, there will be amaximum of 3 hydroxy groups.

The following list exemplifies the hydroxyalkyl groups which areincluded within the definition of R R and R of Formula I above:hydroxymethyl, Z-hydroxyethyl, 3- hydroxypropyl, 2,3-dihydroxypropyl and4-hydroxybutyl. The aryl group may be unsubstituted or may contain anyof a variety of substituents. Typical of the substituents that can bementioned are lower alkyl, halogen, hydroxyalkyl, lower alkoxy, nitro,dialkylamino, carbamoyl, sulfamoyl, etc.

Where the aryl radical is a substituted phenyl radical, the substituentsmay occupy any position in the benzene nucleus. When the aryl radical isa naphthyl radical, the substituents may occupy any of the or or 5positions. In the preferred form of the invention, this aryl radical isa hydrocarbon radical, and more particularly a phenyl radical or a loweralkyl substituted phenyl radical.

By way of illustrating the compounds of this invention of the type inwhich at least one of said R R and R is the radical -alkylene-NHCO-arylor -alkylene-NHSO aryl, the following examples of aryl may be mentioned:phenyl, o-, m-, p-tolyl, m-chlorophenyl, mand p-anisyl, p-ethoxyphenyl,m-hydroxymethylphenyl, m-nitrophenyl, p-dimethylaminophenyl, mcarbamoylmethyl, m sulfamoylmethyl, 1 naphthyl, 2 naphthyl, 3 hyroxy-Z-naphthyl, 8-methoxy-1-naphthy1.

The compounds of the present invention may be prepared by various knownmethods which depend on the nature and position of the substituent-alkylene-X in Formula I.

In the case where R has the value -alkylene-X in Formula 1, thesecompounds are generally prepared by first reacting 2,4dinitrochlorobenzene with a suitable amine, NH -alkylene-X. This isaccomplished by heating one mole of the former with one or more moles ofthe latter, in alcohol, aqueous alcohol, or an organic solventcontaining an acid binder, such as sodium bicarbonate, sodium acetate,calcium carbonate or an additional mole of the amine, at reflux forperiods ranging from /2 hour to 6 hours. This gives an N-substituted2,4- dinitroaniline (Formula A below).

In the next step one of the nitro groups is preferentially reduced togive either a Z-nitro-pphenylenediamine or a 4-nitro-o-phenylenediamine,depending on the reduction method used. In the former case the reductionis carried out essentially by the method of US. Pat. 3,088,978, namelyby catalytic hydrogenation in an organic solvent in the presence ofmineral acid; the acid salt of the substituted2-nitro-p-phenylenediamine (Formula B below) precipitates out of thereaction mixture, and the free base is recovered therefrom bybasification. In order to obtain a 4-nitro-o-phenylenediamine, one canreduce the dinitroaniline (Formula A below) by means of a slight excessof sodium polysulfide in aqueous alcoholic medium by heating at about C.for about 10 to 15 minutes; the product (Formula C below) precipitatesout.

From the substituted nitrophenylenediamines described above, one canproceed to further variations of Formula I in which R and R are alkyl orhydroxyalkyl groups by reaction with the appropriate alkyl orhyroxyalkyl halide, sulfate or tosylate or an alkylene oxide, forexample, with ethyl iodide, dimethyl sulfate, methyl tosylate, ethylenechlorohydrin or ethylene oxide, by known methods. Either one or twoalkyl or hydroxyalkyl groups may be introduced by varying the proportionof the reagent used, the course of the reaction being convenientlyfollowed by chromatogram, and stopped when the appropriate degree ofsubstitution has been reached. Similarly, R and R may be different alkylor hydroxyalkyl groups, which are introduced sequentially by reactionfirst with R -hal and then with R hal (hal being a halogen atom or itsequivalent sulfate or tosylate group).

When in the general Formula I, it is desired that R and/or R be thesubstituted-alkylene-X, the dye may be conveniently prepared from aZ-nitro-p-phenylenediamine or a 4-nitro-o-phenylenediamine (e.g.,Formula D below) in which R is already present. This is reacted with anappropriate X-alkylene-hal, in which hal represents a chlorine, bromineor iodine atom. Depending on the reactivity of the X-alkylene-hal andthe number of X- alkylene groups to be introduced (whether one or two),one uses varying proportions of the reagent, from one mole to a largeexcess.

The reaction is carried out in an organic solvent or aqueous organicsolvent at temperatures varying from room temperature to about C., andfor times varying from 1 to 20 hours. The solvent, temperature and timeof reaction selected depend in part on the activity of the X-alkylenehalused. For example, highly reactive X- alkylene-hal compounds, such aschloroacetonitrile, are reacted at low temperatures, in a low boilingsolvent, such as ethanol, for short times, say 1 to 2 hours. The X-alkylene-hal compounds of low activity, such as chloro ethyl ethylether, are reacted in a high boiling solvent, such as amyl alcohol, atreflux temperature for at least 8 hours.

In any case, the extent of reaction is preferably followed bychromatogram in which can be seen the proportion of unreacted,monosubstituted and disubstituted components, which can be distinguishedby their colors. The reaction is stopped at the desired stage, and themixture worked up as usual. Significant amounts of unreacted startingma- ;Ierial may be removed as the Schiffs base with benzaldeyde.

An alternate method for introducing -alkylene-X groups is to react anitrophenylenediamine (e.g., Formula D below) with a compound having anactivated double bond. In this case the -X moiety generally is anelectron attracting group which serves to activate the double bond.Examples of reactants of this character include acrylonitrile, vinylmethyl ketone, and methyl vinyl sulfone. The reaction is carried out byusing equimolecular amounts of the two materials, in alcohol or aqueousalcohol containing a small amount of acetic acid as catalyst and heatingat reflux for 3 to 10 hours. By this means only one -alkylene-X willgenerally be introduced. For the introduction of two such groups, alarge excess of the unsaturated reactant may be used, serving also asthe solvent. After one group -a1kylene-X has been introduced, it ispossible to introduce a different alkyl, hydroxyalkyl or -alkylene-Xgroup by reaction with the appropriate reagent, e.g., R -hal where halis a halogen atom or an equivalent sulfate or tosylate group.

The following diagrams will illustrate the sequence of reactionsdescribed above:

(a) When R of Formula I is -alkylene-X:

(J1 IIIH-alkylene-X NO; NO; (A)

+ H N-alkylene-X I N0 N0 l IIIH-alkylene-X N|'-alkylene-X NO; NH:

LIYHZ N02 IIIH-alkylene-X IfH-alkylene-X -N02 N RZRB 1 1112113 N 1 (b)When R and/0r R of Formula I is -alkylene-X:

IIIHR N HR;

NO; NO;

-F hal-alkylene-X ----a 111 NH: H-alkylene-X l hal-alkylene-X NHR1 llqHRN01 NO2 I I alkylene-X N (alkylene-X):

Rs (0) When activated double bond reactant is employed: (D) IIIHR; HR

NO; NO;

I IH NH-(iJ-(-X 3=CX/ Rahal l l NHRi N HR;

N02 NO:

I 1 I I i i N(C-C-X) 1% l l a While the above procedures are generallyuseful for the preparation of the dyes of this invention, certainalternate routes may be suitable in specific cases. Thus, when -X isacylamido, one may first prepare an N- aminoalkyl derivative of anitrophenylenediamine, and subsequently acylate the free aliphatic aminogroup by means of an acid anhydride, acid chloride, alkanesulfonylchloride, arylsulfonyl chloride, or chloroformic ester using knownmethods. Or, by reacting 2,4-dinitrochlorobenzene with a diaminoalkane,one can obtain an N- aminoalkyl 2,4 dinitroaniline, which may beacylated and one of the nitro groups reduced and so forth, as describedabove.

When X is a ureido group, NHCONH one may again prepare the aminoalkylderivatives mentioned above, and either react them with potassiumcyanate in a solvent or fuse them with urea for conversion of the freeamino group to the ureido. For introducing the thioureido group, -NHCSNHone may react the aminoalkyl derivatives with carbon disulfide andcaustic to form the dithiocarbonate; this is converted to theisothiocyanate (e.g., by reaction with ethyl chloroformate), and this inturn reacted with dry ammonia.

In the case where X is a sulfamoyl or a substituted sulfamoyl group, itis convenient to first react 2,4-dinitrochlorobenzene with anaminoalkanesulfonic acid (such as taurine), thereby obtaining anN-sulfoalkyl-2,4-dinitroaniline. This may be converted by known methods,as with PCI to the N-chlorosulfonylalkyl 2,4 dinitroaniline which byreaction with ammonia, an alkylamine or a hydroxyalkylamine forms thecorresponding sulfamoylalkyl derivative of 2,4-dinitroaniline.

The dyes embodied in the present invention have many advantages over theprior art dyes utilized in this field. As compared withnitrophenylenediamine dyes having no substituents on the nitrogens,which are yellow or orange in shade, the dyes of this invention show awide range of shade, from yellow to bluish violet.

As compared with the dyes having only unsubstituted alkyl groups on thenitrogen (such as simple methyl, ethyl), the dyes of this invention aremore soluble in water, or more readily dispersible. They can thus givemore concentrated dye baths and therefore much stronger dyeings on hair.Also, as previously mentioned, the dyes of this character wherein only Hor unsubstituted alkyl groups are bonded to nitrogen tend to sublimereadily, when exposed to heat (e.g., body heat or sunlight) and thus tobecome weaker and ofi-shade on wearing. In contrast, the dyes of thisinvention are non-subliming.

As compared to dyes having ionizable substituents on the alkyl groupi.e. where the radical on the nitrogen is (CH2) SO3H, O1 -CH2CH2NR3+C1for example, which ionize in water to give the radicals -CH CO (CH ),,SOor -CH CH NR respectively, the dyes of this invention have much higheraflinity to hair without at the same time dyeing the hair unevenly,rubbing off, or staining the skin.

With regard to prior art dyes having non-ionic substituted alkyl,radicals, such as CH CH OH,

and --CH CONH the advantages of the present dyes vary. For example, anacylated aminoalkyl side chain, such as CH CH NHCOR or would be superiorto the known free aminoalkyl side chain, CH CH NH of the prior art inaffording higher affinity to hair and better wet fastness, includingshampoo fastness. The situation is similar for an alkoxyalkyl group, (CH),,OR, of the present invention, as compared to the known hydroxyalkylgroup, CH CH OH, or the known hydroxyalkoxyalkyl group,

CH CH OCHgCH OH.

This is because dye affinity and wet fastness depend on having anoptimum of hydrophilic character. Thus, too low a hydrophilicity(unsubstituted alkyl) gives low solubility and poor dyeing, but too higha hydrophilicity also gives poor dyeing, since the dye then tends toremain in the dye bath rather than going on the hair. A free hydroxy oramino group has more hydrophilic character than alkoxy or acylamido andcould in fact be too hydrophilic for the purpose of dyeing hair.

A further disadvantage of the aminoalkyl radical is its high basicitywhich makes the dye more soluble in acidic media and less likely to goon hair therefrom. This disadvantage is removed in the case of all ofthe present acylamido derivatives, i.e., alkyl substituted by NHCOR,NHCOAr, NHSO R, NHCONH NHCO R, NHCSNH Another comparison may be madedirectly between the known sulfonic acid dyes (having (CHQ SO H) and thepresent sulfonamide dyes (having SO NH SO' NHR, or SO NRR'). Asdiscussed above, the sulfonic dyes are anionic, with low generalaffinity when compared to the sulfonamides of this invention.

The dyes of the present invention can be employed to prepare basic,neutral or acidic dye compositions and because of their stability, maybe used in conjunction with oxidation dyes. Furthermore, they maylikewise be included in hair dyeing compositions which contain otherdirect dyeing dyes that also may or may not contain an oxidation dye. Avariety of direct dyeing dyes are known in the prior art which areuseful for this purpose. They include other nitro dyes, azo dyes,anthraquinone dyes, etc. By way of illustration, any of the nitro dyesdisclosed in the following U.S. patents may be used in conjunction withthe present nitro dyes: 2,750,326; 2,750,327; 3,088,- 877; 3,088,878 and3,088,978.

The dye compositions of this invention have in general the advantagethat they are stable on storage. For example, when they are stored inthe dark at 50 C. for a period of 3 months and then dyed on hair bymethods described below, they show essentially no change in shade orstrength of dyeing, as compared to the same compositions appliedinitially, before storage. Stability on storage is of great commercialimportance, since dye compositions on the market are likely to be heldon the shelf for pcriods up to several years, sometimes at high ambienttemperatures.

The pH of the dye compositions of this invention can vary from about 2.5to 11. In the acid range the pH of about 3.5 to 6 is suitable. It ispreferred, however, that the compositions be in the alkaline range, andparticularly at a pH of about 7.5 to 10. Any selected water dispersible,compatible, alkalizing agent (if it is desired to have the compositionsin the alkaline range) can be used to give the desired pH. The quantityof the alkalizing agent employed can vary over a wide range depending onthe dye and particular alkalizing agent employed and the desired pH.Illustratively, the alkalizing agent can vary from less than about 0.1%to about 10%, and preferably from about 0.25% to about 5% by weight ofthe composition.

The alkalizing agent is selected so that it will not interfere (i.e., iscompatible) with the dye employed, and will not precipitate the dye orintroduce any possibility of toxicity under the conditions of use, orinjure the scalp at its ultimate concentration in the composition to beapplied to the keratinaceous material. A preliminary test of someselected alkalizing agent can be made to note its compatibility with thedye or to discover possibility of toxicity or injury.

Ammonium hydroxide, because of its freedom from toxicity over a wideconcentration range and its economy, is an acceptable alkalizing agent.However, there can be used in place of, or together with, ammonia anyother compatible ammonia derivative as an alkalizing agent, such as analkylamine, such as ethylamine, dipropylamine, or triethylamine, analkanediamine, such as 1,3-diaminopropane, an alkanolamine, such asethanolamine or diethanolamine, a polyalkylenepolyamine, such asdiethylenetriamine, or a heterocyclic amine, such as morpholine.

Also, as alkalizing agent, any alkaline earth hydroxide, for example,calcium hydroxide or magnesium hydroxide,

can be used up to the limit of its water solubility and at anyconcentration that fails to produce a precipitate with any of thecomponents of the composition. The dissolved alkaline earth hydroxidesare preferred over the alkali metal hydroxides, such as sodium hydroxideor potassium hydroxide, or carbonates, such as sodium carbonate andbicarbonate, any of which can also be used so long as their ultimateconcentration in the final dyeing solution is below that which mightpossibly irritate the scalp.

The alkalizing component of choice, however, is a Water-soluble organicamine of low volatility (B.P. higher than about 50 C.) having less thanabout 12 carbon atoms, such as n-propylamine, isobutylamine, 2ethylbutylamine, diethylamine, triethylamine. Particularly suited as thealkalizing agent are the following: (A) primary aliphatic diamines, suchas ethylenediamine; 1,2 diaminopropane; 1,3-diaminopropane;diethylenetriamine; triethylenetetramine; 2,2-iminodipropylamine; 3, 3'iminodipropylamine; and bis-hexamethylenetriamine; (B) alkanolamines,such as ethanolamine; isopropanolamine; diethanolamine;di-isopropanolamine; triethanolamine; triisopropanolamine;N-methyldiethanolamine; diisopropylethanolamine;dimethylisopropanolamine; 2-amin0- 2 methylpropane-1,3-diol;tris(hydroxymethyl)methylamine and the like, which may also have aphenyl substituent, e.g., N-(2-hydroxyethyl)aniline; N-methyl-N-(Z-hydroxyethyl)aniline; N,N-bis(2 hydroxyethyl)aniline; and (C)heterocyclic amines, such as morpholine, N- mcthylmorpholine,N-ethylrnorpholine, N-hydroxyethylmorpholine, N-phenylmorpholine,piperidine, N-hydroxyethylpiperidine, and piperazine.

The pH of the composition may be adjusted with any inorganic or organicacid or acid salt which is compatible with the composition and will notintroduce toxicity under its conditions of use, especially when acidcompositions are desired. Illustrative of acids or acid salts there canbe mentioned: sulfuric, formic, acetic, lactic, citric or tartaric acid,or ammonium sulfate, sodium dihydrogen phosphate, or potassiumbisulfate.

Water-soluble surface active agents can also be employed in the dyeingcompositions utilized in this invention. These can be anionic, non-ionicor cationic. Illustrative of the various types of water-soluble surfaceactive agents there can be mentioned: higher alkylbenzenesulfonates;alkylnaphthalenesulfonates; sulfonated esters of alcohols and polybasicacids; taurates; fatty alcohol sulfates; sulfates of branched chain orsecondary alcohols; alkyl dimethylbenzyl ammonium chlorides; and thelike. Illustrative of specific surfactants there can be mentioned:lauryl sulfate; polyoxyethylene lauryl ester; myristyl sulfate; glycerylmonostearate; sodium salt of pahnitic methyl taurine; cetyl pyridiniumchloride; lauryl sulfonate; myristyl sulfonate; lauric diethanolamide',polyoxyethylene stearate; stearyl dimethyl benzyl ammonium chloride;dodecyl benzene sodium sulfonate; nonyl naphthalene sodium sulfonate;dioctyl sodium sulfosuccinate; sodium N-methyl-N-oleoyl taurate; oleicacid ester of sodium isothionate; sodium dodecyl sulfate; the sodiumsalt of 3,9- diethyl tridecanol-6-sulfate and the like. The quantity ofwater-soluble surface active agent can vary over a wide range, such asthat of from about 0.25% to 15% and preferably from about 0.25% to 10%by weight of the composition.

A thickening agent can also be incorporated in the present dyeingcomposition which may be one or several of those commonly used in hairdyeing, such as sodium alginate or gum arabic, or cellulose derivatives,such as methylcellulose, or the sodium salt of carboxymethylcellulose,or acrylic polymers, such as polyacrylic acid sodium salt, or inorganicthickeners, such as bentonite. The quantity of thickening agent can varyover a Wide range, such as that of from about 0.1% to 20% and preferablfrom about 0.5% to 5% by weight.

Tinctorially effective quantities of the novel nitro dyes in thecompositions of this invention can also vary over a wide range, such asthat of about 0.01% to greater than about e.g., by weight of thecomposition, and preferably from about 0.01% to about 2% by weight. Thewater content of the composition is ordinarily the major constituent andcan vary over a wide range dependent in large measure on the quantity ofother additives. Thus, the water content can be as little as 10%, andpreferably from about 70% to 99%.

The dyeing compositions of this invention are preferably aqueouscompositions. The term aqueous composition is used herein in its usualgeneric sense as embracing any water-containing composition embodied inthe invention. This includes true solutions of the dye in an aqueousmedium, either alone or in conjunction with other materials, which arealso dissolved or dispersed in the aqueous medium. The term aqueouscomposition also encompasses any mixture of dye with the aqueous mediumeither alone, or together with other ingredients. The dye may becolloidally dispersed in the medium or may merely be intimately mixedtherein.

The term aqueous medium as used herein, includes any medium whichcontains water. Thus, the aqueous medium may be an aqueous alkaline,aqueous neutral or aqueous acid medium. Moreover, the aqueous medium maycomprise water and a solvent, e.g., ethanol. The latter may be employedas a common solvent to enhance the solution of the dye or some otherorganic material.

The aqueous compositions of this invention may take many forms. Thus,they may be thin or thick flowable Any of the dyes, surface activeagents, alkalies, thickening agents, acids and combinations thereof setforth above may be used in the proportions specified in the tableimmediately above.

(2) ACID COMPOSITIONS The acid compositions are similar to the abovealkaline compositions, except that the alkali is omitted, and the acidis added to a pH of 2.5-7, preferred 3.5-6.5. The surfactant may beanionic, cationic or non-ionic or suitable mixtures of these, and any ofthese mentioned above may be used. The choice of thickener is somewhatmore limited, to alkylcellulosics, such as methylcellulose andinorganics. In certain cases the surfactant, itself, acts as athickener.

(3) OXIDATION DYE COMPOSITIONS The novel nitro dyes utilized in thisinvention are generally compatible with oxidation dyes. Accordingly,they can be used in oxidation dye compositions. Suitable compositionscontain 1-5% ammonia, 2-3% hydrogen peroxide or urea peroxide; 0.005% to2% oxidation dye components; 0.001% to 3% Compound I as defined above,as well as surfactants, thickeners, etc. By way of illustration in thisconnection, the following oxidation dye components can be utilized informulating this composition: o-phenylenediamine, m-phenylenediamine,p-phenylenediamine, p-toluenediamine, nitro-p-phenylenediamine,4-nitro-o-phenylenediamine, p-aminodiphenylamine; 4,4-diaminodiphenylamine; 4,6-dinitro 2 aminophenol; 4- nitro-Z-aminophenol;2,4-diaminoanisole, hydroquinone, resorcinol, p-aminophenol;1,2,4-trihydroxybenzene; 1,2, 4-triacetoxybenzene.

The dyeing compositions of this invention can be prepared by theconventional methods used in the hair dyeing art. Thus, they can beprepared by dissolving or suspending the dye in water in the desiredconcentration. Water miscible organic solvents can be employed tofacilitate solution of the dye; in this event, the dye can be dissolvedfirst in the solvent and then diluted with water. The dispersion of thevarious ingredients can also be facilitated by heating the compositionat temperatures varying from 40 C. to C., either before dilution withwater or afterwards.

The dyeing compositions of this invention can be ap plied to hair by theconventional techniques used in the art. lllustratively, when applied toliving hair on the human head, the compositions can be applied to thehair with a brush, sponge, or other means of contact, such as dippinguntil the hair is properly saturated with the composition.

The reaction time or time of contact of the dyeing composition with thehair is not critical and can vary over a wide range used in the hairdyeing art, such as periods of about 5 minutes to about 2 hours, andpreferably from about 15 minutes to about 60 minutes. The dyeingtemperature can vary over wide limits as is conventional in the art.Thus, the dyeing temperature can vary from about room temperature, e.g.,about 20 C. to above about 60 C., and preferably from about 20 C. toabout 45 C.

The following examples are further illustrative of the presentinvention. It is to be understood, however, that the invention is notlimited thereto.

Example 1 NHCH2CH2O CH;

A solution of 37.5 g. 2-methoxyethylamine in 200 ml. water was heated toreflux, and 50 g. 2,4-dinitrochlorobenzene was slowly dropped in. Thissolution was then refluxed for an additional hour, and the mixture wascooled and filtered. The filter cake was then washed with water: Yield,58.8 g. of a product having the above structural formula. This had amelting point of 143-7 C.

Example 2 NHCHaGHi 0 CH8 To a solution of 30 g.N-(Z-methoxyethyl)-2,4-dinitroaniline in 500 ml. 50% isopropanol,maintained at a temperature of 70 C., was added 50 ml. of an aqueoussolution containing 31.5 g. 60% sodium sulfide flakes and 8.2 g. sulfur.The resulting solution was stirred for one hour, then poured over ice.The product was then filtered off and washed. This synthesis gave ayield of 8.2 g. of yellow crystals of the product of the above formulawhich had a melting point of 101-6 C.

was hydrogenated at atmospheric pressure until 3 molar equivalents ofhydrogen were taken up. A precipitate was formed which was filtered 011'and treated with 600 ml. boiling water in order to dissolve the sulfatesalt of the product. The hot slurry was filtered and the filtrate wascooled and made basic with ammonia. The product, which has the abovestructure, and which was in the form of reddish crystals, was filteredoff. The yield was 3.3 g.

was heated at reflux. Over a period of two hours, 320 g. of 25% aqueousNaOH was dropped into the reaction mixture. The excess chloroethanol wassteam-distilled off. The residue was then extracted with ethyl acetate.The solution was then concentrated and, on standing in the cold, therewas obtained 9 g. of violet crystals having a melting point of 645 C.This product has the above structure.

Example 5 IIIHCHzCHzOCHzCHa To a mixture of:

Isopropanol ml 400 Na CO g 2-ethoxyethylamine g 45 at reflux was addedover a period of /2 hour 101 g. of 2,4-dinitrochlorobenzene. Thismixture was heated for one hour, cooled and filtered. The productobtained was then washed with water. There was recovered 124 g. of theproduct of the above structure, having a melting point of 81-2 C.

Example 6 NHOHgCHzOCHzCHa NHZ To a mixture of 30.7 g.N-(2-ethoxyethyl)-2,4-dinitroaniline and 175 ml. isopropanol heated at70-80 C., there was added, while stirring and over a period of one hour,a solution of 31.5 g. of 60% sodium sulfide flakes, 8.2 g. sulfur and 50ml. water. The reaction mixture was cooled, filtered and the product wasrecrystallized from water. This product, having the above structuralformula, was in the form of yellow crystals and had a melting point of82 C.

12 Example 7 ITIHCH CH OCH OH:

A mixture containing:

5% platinum-on-charcoal g 1 N-(2-ethoxyethyl)-2,4-dinitroaniline g 12.7Ethanol ml 75 50% sulfuric acid g 30 was hydrogenated at 50-90 p.s.i.until 3 molar equivalents of hydrogen were absorbed. The mixture wasfiltered and the precipitate extracted with hot water for removal of thesulfate product. The extract after cooling was made basic with ammonia.The product, which has the above structure, was filtered ofi" andrecrystallized from ethanol. This was in the form of red crystals andhad a melting point of 86 C.

Example 8 IITHCH CH O OH; OHa

To a solution of N -(2-ethoxyethyl)-2-nitr0-phenylenediamine in 50 ml.ethanol, 150 ml. chloroethanol was added. Over a period of 2 hours atreflux, there was added 200 g. of 25% aqueous NaOH. Aftersteam-distilling 01f the excess chloroethanol, the residual mixture wasextracted with ethyl acetate. On evaporation of the solvent, there wasobtained a violet dye of the melting point 523 C.

Example 9 NHOHa NHCHzCHzOCH 5 A mixture of 16.7 g. N-methyl-2-nitro-pphenylenediamine, 10.0 g. sodium carbonate, 9.5 g.2-chloroethyl methyl ether, and 150 m1. n-amyl alcohol was heated atreflux for 10 hours. At this point a test portion examined by paperchromatography showed the presence of reddish violet product and asignificant amount of the starting primary amine N methyl 2nitro-p-phenylenediamine; however, no tertiary amine by-product waspresent. The reaction mixture was steam-distilled and evaporated todryness, and the residue dissolved in ml. ethanol. Then, for removal ofthe unreacted primary amine, 10.6 g. benzaldehyde was added, the mixtureheated for 1 hour, and the precipitated benzal derivative of N-methyl-2-nitro-p-phenylenediamine filtered off. Excess benzaldehyde was removedfrom the filtrate by steam distillation, and the desired productextracted using ethyl acetate. The extract was taken to dryness, 50 m1.ethanol added, and HCl gas admitted, thereby precipitating 5.5 g. of thehydrochloride of N -methyl-N -(Z-methoxyethyl)-2-nitrop-phenylenediamineas yellow crystals; this was filtered off and used as such in dyeingexperiments described be low.

13 Example 10 NHOHzOHzNHC OCH:

To 56.5 g. N-(Z-aminoethyl)-2,4-dinitroaniline in 300 ml. water, therewas added 30 g. acetic anhydride. The mixture was heated at 80 C.,cooled and then filtered. The filter cake obtained was then washed.There was recovered 58 g. of acetylated product of the above structurewas hydrogenated at atmospheric pressure until 3 molar equivalents ofhydrogen were absorbed. The reaction mixture was then filtered and theprecipitate was slurried in 100 ml. of water and refiltered for removalof the catalyst. Ammonia Was added to the filtrate until it was basic.Violet crystals were then filtered off which had a melting point of 8790C.; the product has the above structural formula: Calcd for C H N O N,23.5%; Found N, 23.5%.

Example 12 IFIHCHgCHzNHC OHa A mixture of the dye, N-(Z-acetamidoethyl)-2-nitro-pphenylenediamine, 2.5 molar equivalents ofdimethyl sulfate, and 2. molar equivalents of sodium carbonate, in 50%aqueous alcohol, was heated at reflux until no further change wasevident on a paper chromatogram. The alcohol was then distilled OE, andthe mixture cooled. The precipitated product, which has the structureformulated above, was filtered olf, washed and dried.

Example 13 NHCHQCHZNHC CHI A mixture of N-(2-acetamidoethyl)-2-nitro-p-phenylenediamine, 3.5 molar equivalents ofethyl iodide, and 2 molar equivalents of sodium carbonate, in 50%aqueous ethanol were heated in an autoclave at 80-90" C. for about 14hours. The alcohol was then distilled otf, and the product isolated byfiltering and washing. -It has the structure formulated above.

Example 14- NHCHICHZNHCOCH:

2 A mixture of:

N-(Z-acetamidoethyl)-2,4-dinitroaniline g 13.4 Water ml 60 Isopropanolml 60 was heated at 70-80 C. While heating this mixture, there was addeddropwise a solution of:

Sulfur g 4.7 60% Sodium sulfide flakes g a 17.7 Water ml 18 The reactionmixture was cooled, filtered and the precipitate obtained was washedwith water and recrystallized from 50 ml. ethanol. There was obtained5.0 g. of the product of the above structure. This was in the form oforange crystals having a melting point of 198-201" C.; Calcd for C H N ON, 23.5%; Found: N, 23.1%.

Example 15 NHOH CH NHC 0 CH;

A solution of N -(Z-acetamidoethyl)-2-nitro-p-phenylenediamine in 150ml. ethanol was heated to reflux. Ethylene oxide was passed in and thereaction mixture was periodically examined by paper chromatogram(developed with water). When the chromatogram showed the virtual absenceof the red starting material, and the appearance of essentially only aviolet spot, the reaction was terminated. After evaporation of thesolvent, there remained a viscous violet oil which did not crystallizeon standing. The product has the structure formulated above.

Example 16 IIIHGHICHgNH C O CH CHa A mixture of:

N-(Z-aminoethyl)-2,4dinitroaniline g.. 56.5 Water ml 500 Propionicanhydride g 30 was stirred at room temperature for 30 minutes. This wasthen heated to C., cooled, and the precipitate which had formed wasfiltered off, washed and dried. The yield was 49.5 g. and the producthad a M.P. of 156-60 C.

Example 17 lfHCH GH NHC OCH CH;

NH: A mixture containing:

5% platinum-on-charcoal -g 1 Cone. HCl ml 10 N-(2-propionamidoethyl)-2,4-dinitroaniline g 14.1 Ethanol l 200 washydrogenated at about 50 psi. until 3 molar equivalents of H wereabsorbed. A precipitate was formed which was filtered olf, slurried inhot water and then refiltered for removal of the catalyst. To thefiltrate was added ammonia. The product which precipitated was filteredoff. There was obtained 4.5 g. of a product in the form of red crystalswhich had a melting point of 125 7 C.; it has the structural formulashown above.

Analysis.Calcd for C H N N, 22.2%; Found: N, 22.6%.

Example 18 IIIHCHzCHzNHCOCHzCHa Into a solution of:

N -(2-propionamidoethyl)-2-nitro p phenylenediamine g 6.3 Ethanol ml 170was bubbled ethylene oxide until a test portion chromatographed on paperwas essentially homogeneous. After evaporation of the ethanol, there wasobtained a viscous purple liquid which did not crystallize.

Example 19 NHCHzCHzNHC O CHaCHa Into a mixture of:

N-(Z-propionamidoethyl)-2,4-dinitroaniline g 14.1 Water ml 60 Ethanol ml60 heated to a temperature of 70 C. was dropped a solution of.

Sulfur g 4.7 60% sodium sulfide flakes g 17.7 Water ml 18 The mixturewas cooled and a precipitate was filtered from the reaction mixture. Thefilter cake was recrystallized from dilute aqueous ethanol; yield 6.9g.; M.P. 1713 C.; Calcd for C H N O N, 22.2%; Found: N, 22.7%.

Example 20 NHCHQOHZNHO O CHQCHZCHH Into a mixture of:

N(2-aminoethyl) 2,4-dinitroaniline -g-.. 21 Sodium carbonate g 7 Benzeneml 200 at reflux was dropped 12 ml. butyryl chloride over a period of 45minutes. The reaction mixture was cooled and filtered and the cake wasWashed with water and recrystallized from ethanol; yield: 18.6 g.; M.P.180 12 C.; Calcd for C H N 0 N, 18.8%; Found: N, 19.1%.

1 6 Example 21 NHCHZOHZNHCOCHZCHQCHE A mixture of 5%platinum-on-charcoal g 1 Cone. HCl ml 10 Ethanol ml 200N(2-butyramidoethyl)2,4-dinitroaniline g 14.8

was hydrogenated at about 50 p.s.i. until 3 molar equivalents ofhydrogen were absorbed. From the reaction mixture there was isolated 3g. of the hydrochloride salt of the product of the above structure byfiltration and recrystallization from alcohol. It was used as such inthe dyeing experiments described below.

Example 22 I IHOH OH OHQNH,

To a solution of 300 g. 1,3-diaminopropane in 500 ml. ethanol heated atreflux was added 202 g. 2,4-dinitrochlorobenzene. The heating wascontinued for an additional 30 minutes, and the mixture filtered hot inorder to separate the insoluble N,N'-bis(2,4-dinitrophenyl)-1,3-diaminopropane obtained as a by-product. The filtrate Was diluted withcold water and N (3-aminopropyl)-2,4- dinitroaniline (225 g.)crystallized out; M.P. 769 C. This was recrystallized from carbontetrachloride; M.P. 86-7 C.

Analysis.-Calcd for C H N O (percent): C, 45.0; H, 5.00; N, 23.3. Found(percent): C, 45.1; H, 5.18; N, 22.8.

Example 23 lTTHCHgCHgCHgNHCOCHS NO, A mixture of:

N-(B-aminopropyl)2,4-dinitroaniline g 120 Water and ice ml 500 Aceticanhydride was stirred for two hours. The mixture was filtered, and thefilter cake was washed and dried; yield, 90.5 g.; M.P. 149-50 C.

of hydrogen had been absorbed, the hydrogenation was terminated. Themixture was filtered and the hydrochloride of the product was extractedfrom the filter cake with hot water. After removal of the water, theresidue of the hydrochloride was recrystallized from ethanol; yield 3.1g.

Analysis.-Calcd for C H ClN O (percent): Cl, 12.3; N, 19.4. Found(percent): CI, 12.6; N, 19.1.

Example 25 NHCH CH NHCOCH;

A slurry of 19.6 g. N -(2-aminoethyl)-2-nitro-p-phenylenediamine in 150ml. water was treated with 10.2 g. acetic anhydride, and the mixturewarmed gently at 40- 50 C. for minutes, and then at 80 C. for one hour.After cooling the mixture was basified, extracted with ethyl acetate,and the extract dried over anhydrous magnesium sulfate. The ethylacetate was removed and replaced with 100 ml. ethanol. Dry hydrogenchloride was was bubbled in, thereby precipitating the yellow crystalswhich are the hydrochloride salt of the above formulated product. Theywere used as such in dyeing experiments, as described below.

Example 26 III H C H:

1HCH2CH2NH1 A mixture of 16.7 g. N -methyl-Z-nitro-p-phenylenediamine,40.8 g. 2-br0moethylamine hydrobromide, 175 ml. water and 75 ml.isopropanol was treated with sodium carbonate until slightly alkaline;10.6 g. being reqiured. To this was added dropwise over one-half hour,at 75-80 C., a 25% solution of 4.8 g. sodium hydroxide. After reflux foranother hour, the alcohol was distilled off, the

residue cooled, salted, and treated with 2 ml. conc. HCl until justneutral (pH 6-7). The precipitate, which was the free base of theproduct, having the above formulated structure, was filtered 01f, washedwith 5% brine, and then with water. Yield, 12.0 g. of violet crystals,M.P. 62-64 0., having essentially a single colored component by paperchromatography.

Example 27 NHCHI N-(3-aminopropyl)-2,4-dinitroaniline was converted tothe glycolyl derivative by reaction with 1.1 molar equivalent ofglycolic acid in benzene solution in the presence of sodium bisulfate.The mixture was heated at reflux under a benzene-water separator, sothat the water produced during the reaction was so-distilled withbenzene as it was formed, and removed from the reaction mixture. Heatingwas continued until water no longer distilled off. The reaction mixturewas taken to dryness, giving N-(3-glycolamidopropyl)-2,4-dinitroaniline, which was washed with water anddried, and used directly in the next synthetic step.

Example 29 NHCILCH CH NHC O CH OH N (3-glycolamidopropyl)2,4-dinitroaniline was hydrogenated catalytically according to theprocedure of Example 11 for reduction of the 4-nitro group. The product,N (3 glycolamidopropyl)-2-nitro-phenylenediamine, was isolated as thered free base.

Example 30 nnomonmrrooQ To 56.5 g. ofN(2-aminoethty1)-2,4-dinitroaniline in 200 ml. of 5% aqueous NaOH wasslowly added, while stirring, 40 g. of benzoyl chloride. The reactionmixture was then stirred for an additional two hours. The reactionproduct was filtered off and the filter cake Was washed well with water.42 g. of the product, which has the above formulated structure, wasobtained. On recrystallization from aqueous dimethylformamide, it hasthe melting point l88-189 C.

Analysis.Calcd for C H 4N4O N, 17.0%. Found: N, 17.0%.

N 2 benzamidoethyl)-2,4-dinitroaniline g 16.4

was hydrogenated for absorption of 3 molar equivalents of hydrogen. Thereaction mixture was filtered hot to remove the catalyst. On cooling,the hydrochloride of the above formulated product precipitated out andwas collected by filtration, 3.1 g.; M.P. 23 l235 C. From thehydrochloride the free base was recovered; red crystals; M.P. 94 C.

1 9 Example 32 unomonmnoo-Q I I(CHZCHZOH)Z A solution of 5.2 g. N-(2-benzamidoethyl)-2-nitro-pphenylenediamine in 100 ml. of ethanol washeated at reflux and ethylene oxide was passed in until a test portionwas chromatographically homogeneous. The solvent was evaporated oifgiving a thick violet oil which did not crystallize on standing.

To a mixture of N-(Z-benzamidoethyD-Z,4-dinitroaniline g 10 50% aqueousisopropanol ml 70 heated to 60 C. was added a solution of:

60% sodium sulfide flakes ..g.. 15 Sulfur a 4.2 Water ml 30 This mixturewas heated for /2 Hour and then cooled and filtered; the filter cake waswashed with water. Yield 5.3 g.; M.P. 17781 C.

Example 34 lTIHCHzCH CH NHOOCdI A mixture of 56.5 g.N-(3-aminopropyl)-2,4-dinitroaniline, 40 g. benzoyl chloride, and 200ml. sodium hydroxide was vigorously stirred at room temperature for twohours. The product was filtered off, washed with water and dilute acid,and recrystallized from aqueous dimethylformamide. Yield, 46 g., M.P.195-200 C. Cald for C H N O N, 16.3%; Found: N, 16.3%

Example 35 DIIHCHZCH CH NHC o 05H.

N-(3-benzamidopropyl)-2,4-dinitroaniline was hydrogenated by shaking16.4 g. of the material in 200 ml. ethanol, containing 1 gram of 5%platinum-on-charcoal catalyst, and 100 ml. conc. HCl, at about 50 p.s.i.hydrogen, until three molar equivalents of hydrogen were absorbed. Thereaction mixture was filtered to remove the catalyst, and the filtratereduced to a volume of 25 ml. and set in the cold. After some time aprecipitate of 1 g. of the hydrochloride of the above formulated productwas obtained as yellow crystals of M.P. 222-225 C.

Analysis.-Calcd for C H ClN O N, 17.8%. Found: N, 17.9%.

The mother liquor contained considerably more of the NHCHgCH OHNHCHQCHQNHQ To a mixture of:

N Z-hydroxyethyl -2-nitro -p-phenylenediamine g 19.7 Isopropanol mlWater ml 175 2- bromoethylamine hydrobromide g 61.2

neutralized with sodium carbonate to slight alkalinity was addeddropwise at 75 C. to C., over a period of 20 minutes, 6.0 g. sodiumhydroxide in the form of a 25% solution. Refiuxing was continued forone-half hour. Then the alcohol was distilled OE, and the mixture saltedat room temperature and acidified with hydrochloric acid. The lightbrown precipitate which formed was filtered 0E, and washed with a littlewater. Upon recrystallization from ml. boiling water, there was obtained12.0 g. golden yellow crystals of the hydrochloride of N-(2-hydroxyethyl)-N -(2 aminoethyl) 2 nitro-p-phenylene; M.P. 193194 C.,pure by chromatographic analysis.

Example 37 NHCHzCHzOH A mixture of 24.0 g. N -(2-hydroxyethyl)-N (2-aminoethyl)-2-nitro-p-phenylenediamine, 125 ml. 5% aqueous sodiumhydroxide and 15.5 g. benzoyl chloride was vigorously shaken in a bottleat room temperature until the odor of benzoyl chloride had disappeared(about 1 hour). The mixture was then warmed at 40-50 C. for /2 hour forsaponification of any benzoyloxy group which may have formed. Thereaction product was then filtered off, and was in the form of violetcrystals having the above formulated structure.

Example 38 ITIHCHzCHzCHzNHSOzGHa A mixture of 24 g.N-(3-aminopropyl)-2,4-dinitroaniline, 11.4 g. methanesulfonyl chloride,9 g. sodium bicarbonate, and 100 ml. ethanol was heated at reflux for 4/2 hours. The product, which precipitated on cooling, was filtered off,washed with hot water and dried. Yield, 11.5 g; M.P. afterrecrystallization from ethanol, 162- 165 C.

Analysis.-Calcd for C H N O S: N, 17.5%. Found: N, 17.3%

Example 39 IIIHCH CI-IzCHzNHS OzCHz A mthod of 3.18 g.N-(3-methylsulfonamidopropyl)- 2,4-dinitroaniline, 0.3 g.platinum-on-charcoal 2 ml. conc. HCl, and 125 ml. ethanol washydrogenated until three molar equivalents of hydrogen were absorbed. Noprecipitate had formed. The catalyst was filtered off. The filtrate wasevaporated to dryness and the residue dissolved in water. The aqueoussolution was then extracted with ethyl acetate for removal of theby-product, which is an isomer of the desired product. Afterwards, thesolution was made alkaline, and the red dye which partly precipitatedwas extracted from the mixture with ethyl acetate. There was obtained1.8 g. of red dye of the M.P. ll4-7 0., having the structure formulatedabove.

Example 40 NHCH CHgCHzNHS 020E:

The dye, N -(3-methylsulfonamidopropyl)-2-nitro-pphenyleneldiamine, washydroxyethylated by bubbled ethylene oxide through a solution of the dyein ethanol, at reflux temperature. When sufiicient ethylene oxide hadbeen bubbled in, as determined chromatographically by the appearance ofa maximum of a bluish violet spot, the reaction mixture was taken todryness. The residue was recrystallized from aqueous dimethylformamide,and ap peared as dark violet crystals; it has the above designatedstructure.

Example 41 To a solution of 21 g. N-(3-methylsulfonamidopropyl)-2,4-dinitroaniline in 150 ml. ethanol was aded a polysulfide solutionprepared from 14.7 g. sodium sulfide and 3.9 g. sulfur dissolved in 45ml. water. The addition was carried out at 70-80 C. over a period ofone-half hour, and heating was continued for an additional one-halfhour. The reaction mixture was then poured on ice, and the precipitatecollected by filtration, washed with water and dried. It wasrecrystallized from ethanol; yield, 11.6 g.; M.P. 157-160 C.

Example 42 D IHCH CHgNHSOZCHQ N -methyl-N -(2-aminoethyl) 2nitro-p-phenylenediamine was treated with methanesulfonyl chlorideaccording to the procedure of Example 38. There was obtained a bluishred product, N -methyl-N-(2-methylsulfonamidoethyl)-2-nitro-p-phenylenediamine.

Example 43 NHCH;

NOz

HOCH CH NOH CH NHSO CHa The dye, N -methyl-N-(Z-methylsulfonamidoethyl)-2- nitro-p-phenylenediamine, washydroxyethylated by following the procedure of Example 15. There wasobtained a bluish violet dye which dyed hair according to the proceduresdescribed below.

Example 44 IEIHCHgCHgCHgNHSOzCHzCHgCH:

A mixture of:

N(3-aminopropyl)-2,4-dinitroaniline g.. 22 Sodium bicarbonate g.. 9Propanesulfonyl chloride g.... 15 Ethanol ml was heated at reflux for 6hours. The reaction mixture was cooled, filtered and the filter cakerecrystallized from methanol. 5.9 g. of product were obtained; M.P. -2C.

Analysis.Calcd for C H N O S: 16.2%. Found: N, 16.0%.

was hydrogenated according to the procedure of Example 11. There wasobtained 1.0 g. of the product of the above formulated structure, as thefree base; M.P. 139-42 C.; M.P. of the hydrochlorine 21518 C.

Example 46 NHCHgCHgNHS OQCHH5 A mixture of 22.6 g.N-(Z-aminoethyl)-2,4-dinitroaniline, 17.7 g. benzenesulfonyl chloride,10 g. sodium bicarbonate, and 100 ml. ethanol was heated at reflux for 5hours. After cooling, the product, having the above formulatedstructure, was filtered OE and washed with water. Yield, 15.6 g.; M.P.159-160 C.

Analysis.Calcd for C H N O S: N, 15.3%. Found: N, 15.3%.

Example 47 NHCHgCHgNHS 0300115 N-(2benzenesulfonamidoethyl)-2,4-dinitroaniline was hydrogenatedcatalytically, essentially according to the procedure of Example 11, inwhich platinum-on-charcoal is the catalyst, and the hydrogenation iscarried out in alcohol in the presence of conc. HCl. When the reductionwas complete, the product, which had precipitated out as 23 thehydrochloride, was filtered off together with the catalyst, and thenextracted from the catalyst by means of hot water. On concentrating andcooling, the hydrochloride precipitated out of the aqueous medium asyellow needles, from which the red free base was recovered. It has theabove formulated structure.

Example 48 NHomomNHsmmH,

DKOH CH OH);

N -(Z-benzenesulfonamidoethyl) 2 nitro p phenylenediamine was subjectedto hydroxyethylation following the procedure of Example 15, in which ahot ethanolic solution of the starting material is treated with ethyleneoxide. When the reaction was essentially complete, as shown by a paperchromatogram, the solvent was evaporated off. The residue of reddishviolet dye consisted essentially of the compound of the above formulatedstructure, and was used directly in dyeing experiments as describedbelow.

Example 49 IIIHCHzCHzCHzNHCONHa N 03 A mixture of:

G. N(3-aminopropyl)2,4-dinitroaniline 24 Urea 70 was heated for 5 hoursat 150-165 C. Water was added to the reaction mixture to dissolve theexcess urea and the reaction mixture was filtered. 12 g. of the productwas obtained; M.P. 186-9 C.

was hydrogenated as in the previous examples for reduction of the nitrogroup in the 4-position. The hydrochloride of the product did notseparate by crystallization from the reaction mixture. The mixture ofbases was therefore chromatographed on a silica gel column. Developmentwas efiected by a mixture of 90% CHCL; and CH OH. The red band waseluted using the same solvent mixture, giving 0.7 g. of the product inthe form of dark red crystals; M.P. 173-6 C.; it has the aboveformulated structure.

Example 51 NHCH CH GH NHC ONE;

l uomon on Into a solution of 4 g. N -(3-ureidopropyl)-2-nitro-p- 24phenylenediamine in ethanol at reflux was bubbled ethylene oxide until atest portion chromatographed on paper showed essentially a single violetband. On evaporation to dryness there was obtained a violet viscousproduct which was used directly in the dyeing of hair, described below.

Example 52 IIIHCH CH CH NHCONH To a solution of 28 g.N-(3-ureidopropyl)-2,4-dinitroaniline in 75 ml. 50% isopropanolmaintained at -75 C. was added dropwise, over one-half hour; a solutionof 19.3 g. fused 60% sodium sulfide flakes and 5.1 g. sulfur in 30 ml.water. After additional heating for one-half hour and cooling, thereprecipitated the product, of the above designated structure; it wasfiltered off, washed with water and dried. The orange product was usedas such in the dyeing of hair, as described below.

Example 53 NHCHZCHQNHO ONH,

No. A mixture of N-(Z-aminoethyl)-2,4-dinitroaniline and 5 molarequivalents of urea was fused at 150-160 C. for 5 hours. The excess ureawas then extracted with water, and the product was filtered, thoroughlywashed and dried. It was used as such in the next synthetic step.

Example 54 NHCHzCH2NHC ONH:

N-(2-ureidoethyl)-2,4-dinitroaniline was reduced catalytically accordingto the procedure of Example 50. The product was separatedchromatographically on a silica gel column as in that example, and wasobtained as red crystals having the above formulated structure Example55 NHOH OH NHCSNH To a mixture of 7.6 g. carbon disulfide and 4.0 g.sodium hydroxide in ml. water was added portionwise 22.6 g.N-(Z-aminoethyl)-2,4-dinitroaniline with vigorous stirring andoccasional cooling. When addition was complete, the reaction mixture waswarmed at -90 C. for about 2 hours. It was then allowed to cool to 34-40C., and 10.8 g. ethyl chloroformate was added dropwise with no furthertemperature control. The reaction mixture was stirred until the exothermwas complete and the mixture had cooled down to room temperature. Theprecipitated solid, 2-(2,4-dinitroani1ino)ethyl isothiocyanate, wasfiltered ofi, Washed with aqueous alcohol and water and dried.

The above isothiocyanate was dissolved in ethanol and dry ammonia gaswas bubbled through the solution. The exotherm brought the solution toreflux temperature, and

it was allowed to reflux for an additional hour. Part of the alcohol wasthen distilled oil, the mixture poured on ice, and the product collectedby filtration, and washed with water and dried. The product wasN-(Z-thioureidoethyl)2,4 dinitroaniline having the above formulatedstructure, and was used directly in the next synthetic step.

Example 56 IIIHCH CH NHCSNHg The compound, N-(Z-thioureidoethyl)2,4-dinitroaniline (product of Example 55), was reduced catalyticallyaccording to the procedure of Example 50. In this case also thehydrochloride of the product did not crystallize out of the reactionmixture. The reaction mixture, after removal of the catalyst, wastherefore made basic with ammonia, and extracted with ethyl acetate forrecovery of the mixed primary amines obtained. The mixed amines werechromatographed on a column of silic gel, using chloroformmethanol 9:1for development. The red band was cut out of the column and the productextracted therefrom. It appeared as dark red crystals and had the abovedesignated structure.

Example 57 NHGHzCHzNHC 02021115 N-(Z-aminoethyl)-2,4-dinitroaniline wastreated with one molar equivalent of ethyl chloroformate in pyridinesolution by stirring the mixture of components at room temperature forabout one hour. The reaction mixture was then drowned in water and theprecipitated product N-(2- carbethoxyaminoethyl) 2,4 dinitroaniline,filtered oil, washed and dried.

Example 58 NHCHzCHzNHC 020211;

The compound, N-(Z-carbethoxyaminoethyl)-2,4-dinitroaniline washydrogenated according to the procedure of Example 24. The hydrochlorideof the product having the above formulated structure was recovered asyellow crystals, and was used directly in the dyeing experimentsdescribed below.

Example 59 To a solution of 62.5 g. taurine and 4.2 g. sodiumbicarbonate in 400 ml. water heated at reflux was added slowly 101 g.2,4-dinitrochlorobenzene. Heating was continued for an additional 3hours. After cooling the precipitated crystals were filtered off,pressed dry and recrystallized from hot water containing a small amount(about 1%) of sodium hydroxide. The product isN-(Z-sulfoethyl)-2,4-dinitroaniline.

Example 60 NHCH: CHZS OZNHZ To a slurry of 20 g.N-(2-sulfoethyl)-2,4-dinitroaniline in ml. dry xylene was added 15 g.PCI and the mixture was heated at reflux for 5 hours. The reactionmixture was then poured on ice, and the precipitate filtered olf. Thefilter cake was pressed dry, then stirred with an excess of conc.aqueous ammonia over night at room temperature. The product was filteredoif and recrystallized twice from water. There was obtained 1.8 g. of N-(2-sulfamoylethyl)2,4-dinitroaniline; M.P. -9 C.

Analysis.-Calcd for C H N O S (percent): N, 19.3; S, 11.0. Found(percent): N, 18.7; S, 10.7.

Example 61 NHCHg CHZS ogN I To a solution of 7.3 g.N(2-sulfamoylethyl)2,4-dinitroaniline in 20 ml. 50% isopropanol at 70 C.was added with stirring over a period of 20 minutes a solution of 6.3 g.60% sodium sulfide flakes, and 1.7 g. sulfur in 10 ml. water. Heatingwas continued for an additional onehalf hour. On cooling, the product,which had the above formulated structure, precipitated out and wasfiltered off. It was recrystallized from ethanol; dark orange crystals,M.P. 216218 C.

Example 62 IFTHCEQCH S O NH;

A mixture of 1 g. N-(2-sulfamoylethyl)-2,4-dinitroaniline, 0.1 g. 5%platinum-on-charcoal, 1 ml. conc. HCl, and 100 ml. methanol washydrogenated at atmospheric pressure and room temperature until 250 ml.hydrogen gas was absorbed. The catalyst was filtered ofl, and uponconcentration of the filtrate the product precipitated out as thehydrochloride salt, which was filtered OE and washed with a minimum ofmethanol. It was chromatographically pure, and was the hydrochloride ofthe product formulated above.

Analysis.-Calcd for C8H13CIN404Z N, 18.8%. Found:

The free base was red.

Example 63 NHCH OH SOzNH,

The dye, N -(2-sulfamoylethyl) 2 nitro-p-phenylene diamine was treatedwith 2.5 molar equivalents of dimethyl sulfate and 2 molar equivalentsof sodium carbonate in 50% aqueous ethanol. The mixture was heated atreflux until no further change was observed in the chromatogram. Afterdistillation of most of the alcohol, the product was recovered byfiltration; it was washed and dried.

The dark violet product was used as such for the dyeing of hair, asdescribed below.

Example 64 NHCH OH CO NHOH;

DIIOI The procedure of Example 60 was followed except that in place ofammonia there was used an excess of 40% aqueous methylamine. The productwas N-[Z-(methylsulfamoyl)ethyl]-2,4-dinitroaniline.

Example 65 NHCH CH SO NHCH;

The procedure of Example 62 was followed except that the dinitroanilinederivative used was N-[Z-(methylsulfamoyl)ethyl]-2,4-dinitroaniline. Theproduct was the hydrochloride of the dye of the above formulatedstructure. This salt was used directly in the subsequent hair dyeingexperiments, described below.

Example 66 NHCHgCHgSOzNHCHZCHgOH The procedure of Example 60 wasfollowed except that in place of ammonia there was used an excess of 50%aqueous ethanolamine. The product wasN-[2-(2-hydroxyethylsnlfamoyl)ethyl]-2,4-dinitroaniline and was used inthe next example.

Example 67 NHCH: CHzS O2NHCH2CH OH The procedure of Example 62 wasfollowed except that the dinitroaniline derivative used wasN-[2-(2-hydroxyethylsulfamoyl)ethyl]-2,4 dinitroaniline. The product wasthe hydrochloride of the dye having the above formulated structure. Theyellow hydrochloride product was used in the later hair dyeingexperiments.

Example 68 NHCHgCHi 5 ON (01 The procedure of Example 60 was followed,except that in place of ammonia there was used an excess of 25% aqueousdimethylamine. The product was N-[2- (dimethylsulfamoyl)ethyl]-2,4-dinitroaniline. It was used in the following example.

28 Example 69 N HGHzCHg S O N (CH 3 Hydrogenating was carried outaccording to the procedure of Example 62, except that the dinitroanilinederivative used was N-[Z-(dimethylsulfamoyl)ethyl]-2,4dinitroaniline.The product isolated was the hydrochloride corresponding to the aboveformulated structure. This product was used as such in the dyeingexperiments mentioned below.

Example 70 NHCHgCHgSOgN (011 0112011 The compound,N-[2-(bis-Z-hydroxyethylsulfamoyl) ethyl]-2,4-dinitroaniline washydrogenated according to the procedure of Example 62. There wasobtained the hydrochloride of the base whose structure is formulatedabove. It was used in this form for the dyening of hair, as describedbelow.

Example 71A CHzCHzOH N0 The procedure of Example 60 was followed exceptthat in place of ammonia there was used 25 aqueous Z-methylaminoethanol.The product was N-[2-(N-methy1- N-Z-hydroxyethylsulfamoyl) ethyl]-2,4-dinitro aniline.

Example 713 CH3 NHCHzCHzSOzN CHgCHZOH NO;

The compoundN-[2-(N-methyl-N-Z-hydroxyethylsulfamoyl)ethyl]-2,4-dinitroaniline washydrogenated according to the procedure of Example 62. There wasobtained the hydrochloride of the base whose structure is formulatedabove. it was used in this form for the dyeing of hair, as describedbelow.

Example 72 IIIHCHz CHZS O2 CH3 A solution of 25 g. Z-aminoethylmethylsulfone, in 200 ml. isopropanol containing 8.4 g. sodium bicarbonate washeated at reflux temperature. To the mixture was added dropwise 10.2 g.2,6-dinitrochlorobenzene over a period of one-half hour. The reactionmixture was heated at reflux for another hour. About half the alcoholwas distilled oil and water added, thereby precipitating the productwhose structure is shown above. It was filtered off, washed with aqueousisopropanol, then with water, and dried. The product was used withoutfurther purification in the next synthetic step.

Example 73 NHCH CHzSO CHs The compoundN-(2-methylsulfonylethyl)-2,4-dinitroaniline was hydrogenated accordingto the procedure of Example 47. The product, of the structure formulatedabove, was isolated as the yellow hydrochloride as in that example. Itwas chromatographically pure, and was converted to the red free base forthe dyeing experiments performed on hair, which are described below.

Example 74 IIIHCH:

b'IHCH CH COCH A solution of N -methyl 2 nitro-p-phenylenediamine and 5g. methyl vinyl ketone in 100 ml. ethanol was heated at reflux for 5hours. The chromatogram at this point showed a single, violet componentto be present. The reaction mixture was clarified, and concentrated to75 ml. on cooling, the product, which had the above formulatedstructure, crystallized out. There was obtained 5 g. of red crystals ofM.P. 120-123" C., which was essentially pure by chromatogram; Calcd forC H N O N, 17.7%; Found: N, 17.2%.

Example 75 IIIHCH:

I HOCHzCHzNCHzCHzC OCH:

The dye, N -methyl-N -(3 oxobutyl) 2 nitro-pphenylenediamine (product ofExample 74) was hydroxyethylated by treatment with ethylene oxideaccording to the procedure of Example 15, except that methanol was usedas the solvent instead of ethanol. When the reaction was terminated, asindicated by no further change in a chromatographic test, the reactionmixture was chromatographed on a silica gel column, developing with amethanolchloroform 1:9 mixture. The product, having the structureformulated above, was recovered from the bluish violet band found on thecolumn, and was used for the dyeing of hair as described below.

Example 76 I N(CHaCH COOHa)2 A mixture of 15.3 g.2-nitro-p-phenylenediamine, 14 g. methyl vinyl ketone, and 150 ml.ethanol was heated at reflux for 8 hours. Afterwards it was allowed tocool over night, and the crystalline precipitate filtered off. Thesecrystals showed a single, violet band when examined chromatographically.They were recrystallized from ethanol, giving 15 g. violet crystals,M.P. 7 C.

Analysis.Calcd for C H N O (percent): C, 57.4; H, 6.48; N, 14.3%. Found(percent): C, 57.4; H, 6.73; N, 14.0%.

Example 77 NHCH CH OH The hydrochloride of N-(2-hydroxyethyl)-2-nitro-pphenylenediamine was treated with 4 molarequivalents of methyl vinyl ketone in alcohol under reflux. When thereaction was essentially complete, the mixture was concentrated to asmall volume and, on cooling, the product which has the structuredesignated above, precipitated out, and was filtered off. The purplecrystals were used to dye hair as described in later examples.

Example 78 NHCH:

The compound, N -methyl 2 nitro-p-phenylenediamine, was treated with 4molar equivalents of hydroxymethyl vinyl ketone according to theconditions and procedure of Example 76. There was obtained the producthaving the above formulated structure as a violet powder which was usedin the dyeing experiments described below.

was heated under reflux at 92 C., and over a period of 20 minutes, 45.2g. of chloroacetonitrile was added drop- Wise at this temperature. Afteran additional 15 minutes at reflux, the mixture was allowed to cool,diluted with three volumes of water and salted with NaCl. Thecrystalline substance which separated out was filtered off, washed withwater and recrystallized from 1500 ml. of boiling water, with theaddition of some active carbon. The yield of product, having the aboveformulated struc- 31 ture was 8.5 g.; M.P. 151-152 C. It was essentiallypure by paper chromatography.

Example 80 NHOHzOHaOH NHCHZCN To a mixture of:

N (2 hydroxyethyl) 2 nitro p phenylenediamine g 19.7 Isopropanol ml 75Pyridine g 47.4

was added dropwise, at reflux during /2 hour 45.3 g. chloroacetonitrile.After refluxing for another /z hour, the reaction mixture was dilutedwith two volumes of water and one volume of ice and some salt added. Thecrystalline product which precipitated was filtered olf, and washed toneutrality with cold water. The wet cake was then recrystallized from1350 ml. of boiling water, with the addition of active carbon. Yield:13.2 g. of black crystals; M.P. 120-2 C.

Analysin-Calcd for C H N O' N, 23.7%. Found: N, 23.1%.

Example 81 I\IIHCHQCHQCN A mixture of:

2-nitro-p-phenylenediamine ....g 30.6 Calcium carbonate 1 g 203-bromopropionitrile g 27 Benzene ml 500 was heated at reflux for 13hours. On cooling there crystallized out a red product, which wasrecovered by filtration and recrystallized from ethyl acetate; M.P. 132-133 C. This was the compound shown structurally above. Analysis.-Calcdfor CgH N 0 Z N, 27.2%. Found:

Example 82 NHOH CHgOH biHCHfiHgON A mixture of:

N (2 hydroxyethyl) 2 nitro p phenylenediamine g 9.863-bromopropionitrile ....g 20.1 Na O0 anhydrous g 3.0 Isopropanol ml 50Water ml 35 was heated at reflux for 5 hours. After about 2 hours moreNa CO (2.5 g.) and more bromopropionitrile (5 g.) were added. When thereaction was complete, the mixture was diluted with 50 ml. water, andallowed to stand overnight. Crystals of product separated (5.2 g.crude), which were recrystallized first from 1:3 ethanolwater and thenfrom 9 6% ethanol. Yield: 3.5 g. of small metallic crystals, M.P. =69-70C. The product which has the structure designated above, was homogeneousby chromatogram.

32 Analysis.-Calcd for C H N O N, 22.4%. Found: N, 22.4%.

Example 83 NHOH CH OH HOCHzCH l VGHzCH CN A mixture of 4.38 g. of thedye, N -(2-hydroxyethyl)- N (2-cyanoethyl) 2 nitro-p-phenylenediamine,6.04 g.

2-chloroethanol, 2.5 g. calcium carbonate and 24 ml. water, containingcatalytic amounts of iodine and cuprouschloride was heated at reflux for12 hours. The reaction mixture was then acidified, clarified, dilutedwith three volumes of water, and made alkaline. Upon cooling, theproduct precipitated, and was collected by filtration, M.P. 111-113" C.

in 35 ml. water and 50 ml. isopropanol was heated at reflux. After about2 hours additional sodium carbonate (2.5 g.) and bromopropionitrile (10g.) were added. The total time of refluxing was 5 hours. On cooling andstanding overnight crystals separated, which were filtered 01f andwashed by slurrying in 250 ml. water. Yield: 5.4 g. of small metallicneedles, M.P. 13'Z-134 C. The product which has the above formulatedstructure showed a single, violet component by chromatogram.

Analysis.Calcd for C H N O N, 25.4%. Found: N, 25.1%.

Example NHGHa I HOCHZCHgNCHgCHgON The dye, N -methyl-N-(Z-cyanoethyl)-2-nitro-p-phenylenediamine (product of Example 84) washydroxyethylated by treating it in 50% aqueous ethanol with 3 molarequivalents of ethylene chlorohydrin in the presence of 1.5 molarequivalents of calcium carbonate. The reaction slurry was stirred atreflux temperature until a chromatographic test showed no furtherchange. The mixture was then cooled, acidified to dissolve anycalciferous residue, and steam-distilled for removal of the excesschlorohydrin. On basifying and salting, the product, which has thestructure formulated above, was precipitated and was recovered byfiltering and washing, as violet crystals.v

The following examples illustrate the dyeing of hair with compositionscontaining the dyes described above.

The dyeing procedures used are identified as follows:

DYEING PROCEDURE A.DYEING I-LAIR WITH ALKALINE COMPOSITIONS (pH 7 ORHIGHER) A mixture was prepared using specified amounts of the followingcomponents:

Thickening agent (1) 1 Amount to be specified.

The dye was first wet with isopropanol and the above listed agents wereadded, as well as 50 ml. water. The mixture was then heated at 60 C.with stirring until a uniform dispersion was obtained. The mixture wasthen further diluted with water to a volume of 100 ml. and citric acidwas added to give a final, specified pH of 7 or higher. The dyeingcomposition so obtained was poured on natural gray hair and on bleachedhair and allowed to remain in contact with the hair for 20 minutes at 30C. Afterwards, the hair was rinsed in clear water and dried.

DYEING PROCEDURE B.DYEING HAIR WITH ACID COMPOSITIONS (pH 7 OR LOWER) Amixture was prepared as follows:

Dyeamount to be specified. Isopropanol0.5 ml.

Surface-active agent-amount to be specified. Thickening agentamount tobe specified. Water to 100 ml.

Acid agent to give specified pH of 7 or lower.

The dye was wet with isopropanol, and the other ingredients added withstirring and warming below 50 C. to give a uniform dispersion. Hair wasdyed with this composition as in Procedure A.

PROCEDURE C.--DYEING HAIR FROM Water to 100 ml.

A 30-ml. portion of this composition was mixed with 30 ml. of 6%hydrogen peroxide and the mixture poured on natural gray and bleachedhair and allowed to remain there for 40 minutes at 30 C. The hair wasthen rinsed with clear water, shampooed and dried.

Example 86 The product of Example 2 was dyed on hair according toProcedure A, using 0.25 g. dye, 3.0 g. N-phenyldiethanolamine (asalkaline agent), 3.0 g. sodium N-coconut acid N-methyl taurate (assurfactant), and 3.0 g. hydroxycthylcellulose (as thickener), the pHbeing adjusted to 9.5. Both gray and bleached hair were dyed in stronglevel orange shades fast to shampooing. When this composition was storedfor 3 months at 50 C. and again dyed on hair, the dyeings were fullyequivalent to the initial dyeings in shade and strength.

When the same dye was applied according to Procedure B, using 0.25 g.dye, 1.0 g. nonylphenoxypoly(ethyleneoxy) ethanol (surfactant), 2.0 g.hydroxyethylcellulose (thickener) and citric acid to pH 5, the gray andbleached hair were also dyed uniformly and strongly in orange shade,stable to shampooing. This composition was also unaffected by storage at50 C. for 3 months.

When the dye was applied by Procedure C, it gave similar orange shadesas above, showing its stability to peroxide.

Example 87 The product of Example 3 was dyed on hair according toProcedure A, using 0.3 g. dye, 3.0 g. diethylenetriamine (alkalineagent), 4.0 g. lauric diethanolamide (surfactant) and 3.0 g.methylcellulose (thickener), the pH being adjusted to 8.5. A red dyeingof good strength was obtained, somewhat stronger on the bleached than onthe gray hair, and both fast to shampooing. When the above compositionwas stored at 50 C. for 3 months and then again dyed on hair, the dyeingwere similar in shade and strength to the initial dyeings.

Example 88 The product of Example 8 was dyed on hair according toProcedure A, using 0.15 g. dye, 4.0 g. ethanolamine (alkaline agent),2.0 g. sodium dodecylbenzenesulfonate, and 3.0 g. sodiumcarboxymethylcellulose, the final pH being 8.0. Both gray and bleachedhair were dyed similar shades of bluish violet having good fastness toshampooing and rubbing. The dye composition was also stored at 50 C. for3 months and thereafter dyed hair identically to the initial dyeing inshade and strength.

When Procedure B was used with the same dye, using 0.4 g. dye, 2.0 g.ethyleneglycolmonostearate, 2.0 g. methylcellulose, and lactic acid topH 5.5, the bleached hair was dyed strongly and the gray hairmoderately, in level bluish violet shades, fast to shampooing.

Example 89 The dye which is the product of Example 14 was appliedaccording to Procedure A, using 0.2 g. dye, 3.0 g. isopropanolamine asthe alkaline agent, 4.0 g. coconut acid monoethanolamide (surfactant),3.0 g. hydroxyethylcellulose, and citric acid to pH 7.5. The dyeingswere strong orange shades, similar on both kinds of hair, and fast toshampooing and rubbing. When the pH was adjusted to 9.5, the dyeing weresimilar.

The same dye was applied by Procedure B using the same quantity of dye,3.0 g. polyoxyethylated nonylphenol and 3.0 g. methylcellulose, andacetic acid to pH 6.0. Orange dyeings of good strength and uniformitywere obtained, fast to shampooing.

When the dye was applied by Procedure C, it also gave strong orangedyeing on both gray and bleached hair from the peroxide bath, equal tothe above dyeing applied without peroxide.

Example 90 The product of Example 17 was dyed according to Procedure A,using 0.1 g. dye, 4.0 g. triethanolamine (alkali), 0.75 g. sodiumN-methyl-N-oleoyltaurate (surfactant) and 3.0 g. sodiumcarboxymethylcellulose, and adjusting the pH to 10. A heavy red shade onboth kinds of hair was obtained which was only slighfly reduced after 3shampooings. The dye composition was stable on storage at 50 C. for 3months; thereafter it dyed hair in the same shade and strength asinitially.

When Procedure A was followed using 0.1 g. of the same dye, 0.2 g.triethanolamine (as alkali), 4.0 g. coconut monoethanolamide, and 4.0 g.polyethyleneoxy stearate as surfactants, and adjusting the pH to 7.0, ared shade again was obtained, slightly weaker than the above shade, butremarkably level, and about equal on both kinds of hair.

By following Procedure B, and using 0.1 g. of the same dye, 1.0 g.isooctylphenyl polyethoxy ethanol, and no thickening agent, andadjusting the pH to 5.5 by addition of acetic acid, there was againobtained a strong red dyeing, somewhat stronger on bleached than on grayhair, and fast to shampooing and rubbing.

Procedure C was followed with 0.1 g. of the same dye and gave a reddyeing somewhat weaker than the dyeing mentioned in the first paragraph,but still moderately strong and uniform on. both kinds of hair.

Example 91 The dye product of Example 24 was dyed according to ProcedureA: 0.2 g. dye was combined with 3 g. ethanolamine (alkali), 3 g. sodiumN-coconut acid N-methyl taurate (surfactant) and 2 g. methylcellulose,at pH 8.5. The dyeings were strong reds on both gray and bleached hair,fast to shampooing and rubbing. When, by Procedure A, 0.2 g. dye wascombined with 4 g. 3,3-iminodipropylamine, 2 g. sodium lauryl sulfateand 3 g. methylcellulose at pH 9.5, very similar dyeing were obtained.Again, by Procedure A, for 0.2 g. dye, using 9 g. 28% ammonia as thealkaline agent, 20 g. oleic acid, 1 g. sodium lauryl sulfate and 3 g.polyethoxylated nonylphenol as the surfactants, at pH 9.5, the dyeingswere somewhat weaker than the preceding dyeings, but still strong redson both kinds of hair.

The same dye was applied by Procedure B, in the following compositions:(a) 0.25 g. dye, 3 g. polyethoxylated nonylphenol, 3 g. methylcellulose,and sulfuric acid added to pH 5; (b) 0.25 g. dye, 0.5 g. ethyleneglycolmonostearate, 2 g. dicoco dimethyl ammonium chloride, 1 g. cetyl stearylalcohol, and citric acid added to pH 7. Red dyeings were obtained inboth kinds of hair, of same shade, and almost as strong, as the firstdyeing above obtained by Procedure A. The dyeings were fast toshampooing and rubbing.

The same dye (0.25 g.) was also applied by Procedure C, and in spite ofthe presence of peroxide gave strong red dyeings of gray and bleachedhair.

Example 92 The dye product of Example 32 was dyed by Procedure A, using0.25 g. dye, 2.0 g. N-phenyldiethanolamine (alkali), 3.0 g. coconutdiethanolamide (surfactant) and 1.0 g. co-polymer of acrylic acid andallylsucrose (thickener), the pH being set at 9.0. The color on hair wasbluish violet, the afiinity being high on gray hair and very high onbleached. Shampoo fastness was excellent. The dye bath stored at 50 C.,for 3 months, gave no change in shade and strength of dyeing thereafter.

The same dye by Procedure B, using 0.25 g. dye, 2.0 g. ethyleneglycolmonostearate (surfactant) and ammonium sulfate added to give a pH of5.0, gave a strong bluish violet dyeing of bleached hair, somewhatweaker on gray hair, both dyeings being fast to shampooing and rubbing.

When Procedure B was followed using 0.25 g. dye and 2.0 g. distearyldimethyl ammonium chloride and 1.5 g. cetyl-stearyl alcohol assurfactants, with no thickener, the pH being adjusted to 7 by means ofcritric acid, there was obtained a strong dyeing of the bleached hair inbluish violet shade; the gray hair was dyed a weaker but level shade ofbluish violet, both dyeings being fast to shampooing and rubbing.

Example 93 The dye product of Example 41 was applied to hair byProcedure A, using 0.15 g. dye, 3.5 g. 1,3-diaminopropane (as alkalineagent), 1.0 g. sodium lignosulfonate (surfactant), and 3.0 g.hydroxyethylcellulose (thickener) and setting the pH at 8.0. Both grayand bleached hair were dyed equally strong shades of orange, very fastto successive shampooings. The dye bath was stable on 3 months storageat 50 C.

By Procedure B, this dye, 0.2 g., with 2.0 g. polyethoxylated octylphenol and 2.0 g. hydroxyethylcellulose at a pH of 6.5 effected byaddition of formic acid, gave equal umform orange dyeings of the twokinds of hair fast to shampooing.

Example 94 The product of Example 50 was dyed by Procedure A using 0.1g. dye, 2.0 g. 3,3'-imino-dipropylamine (as alkaline agent), 3.0 g.mixed fatty acids diethanolamide (as surfactant), and 2.0 g. sodiumalginate (as thickener), the pH being adjusted to 9.0. The gray andbleached hair were both dyed a similar, level red shade of goodstrength, which was fast to successive shampoos. The dye compositionsremained unchanged after three months storage at 50 C., after which timeit dyed hair in the same shade and strength as initially.

Procedure A was again followed with this dye, using 0.1 g. dye, 1.5 g.diethylenetriamine (alkaline agent), 2.0 g. N-lauryl myri'stylbeta-aininopropionic acid (surfactant), and 1.0 g. methylcellulose, at apH of 8.0. The dye ings were similar to those above.

In a third dyeing by Procedure A, 0.1 g. of the same dye, was combinedwith 2.5 g. morpholine (alkaline agent), 2.0 g. dodecylbenzenesulfonate(surfactant) and 1.0 g. copolymer of acrylic acid and allylsucrose(thickener) at a pH of 9.5. The dyeings were similar to those above. 1

Example The dye product of Example 61 was applied to hair by ProcedureA, using 0.2 g. dye, 1.5 g. ethylenediamine (alkaline agent), 0.75 g.sodium lauryl sulfate (surfactant), and 2.5 g. sodiumcarboxymethylcellulose, at a pH of 9.5. A strong level orange dyeing wasobtained on both kinds of hair, fast to shampooing and rubbing.

When dyed by Procedure 13, with 0.2 g. dye, 3.0 g. cetylpyridiniumbromide (surfactant), 1.5 g. methylcellulose and tartaric acid added topH 6.5, the dyeings were slightly stronger than the above dyeings, butequally level and uniform as between the two kinds of hair.

The same dye was applied by Procedure C in which case it gave stronglevel dyeings. The shade and strength were the same as when the dye wasapplied without the use of hydrogen peroxide, substituting an equalvolume of water.

Example 96 The product of Example 62 was dyed variously according toProcedure A, using 0.25 g. dye. In one case the alkaline agent was 0.5g. triethanolamine, the surfactant was 2.0 g. sodiumN-oleoyl-N-methyltaurate, and the thickening agent was 3.0 g. sodiumcarboxymethylcellulose, the pH being adjusted to 7.5. In another casethere was used 2.0 g. N-phenyldiethanolamine, 2.5 g. polyoxyethylenelauric ester, and 3.0 g. sodium carboxymethylcellulose and the pH was8.5. In both cases very similar red dyeings were obtained, of about thesame shade and strength on the two kinds of hair, and fast toshampooing.

Example 97 The dye product of Example 74 was applied to hair byProcedure A using 0.15 g. dye, 3.0 g. diisopropanolamine, 3.0 g. lauricdiethanolamide, and 3.0 g. methylcellulose, at pH 8.5. An excellentmaroon dyeing was obtained of high strength and levelness, fast to threesuccessive shampooings. When in this procedure there was used 2.0 g.1,3-diaminopropane, 3.0 g. glyceryl stearate and 3.0 g. methylcellulose,at pH 9.0, the dyeings were essentially similar in shade, strength andfastness. When the above dye compositions were stored at 50 C. for 3months and then dyed on hair again, the dyeings were similar to theinitial dyeings in shade and strength.

The dye was also applied by Procedure B using 0.15 g. dye, 2.0 g.ethylene glycol monostearate, and lactic acid added to give pH 5.0. Thebleached hair was dyed strongly maroon, the gray hair being dyed asimilar but weaker shade. The same procedure was followed using thefollowing ingredients: 1.0 g. polyethoxylated coconut fatty acid amide,3.0 g. di-coco dimethyl ammonium chloride, 2.0 g. hydroxyethylcellulose,and citric acid to give pH 6.5. Moderately strong maroon dyeings wereobtained, with the bleached hair being dyed stronger than the gray.

Example 98 The product of Example 76 was dyed on hair by Procedure A,using 0.2 g. dye and the following adjuvants: 2.5 g. diethylenetriamine,2.0 g. polyoxyethylene lauric panolamine, 3.0 g. coconut fatty aciddiethanolamide and 3.0 g. sodium carboxymethylcellulose, at pH 8.0.

The same dye was also applied by Procedure B using: 0.2 g. dye, 1.5 g.glycerol monooleate and acetic acid added to give a pH of 5.5. A similarshade of violet was obtained which was particularly strong on thebleached hair.

Example 99 The dye product of Example 81 was applied by Procedure Ausing 0.15 g. dye and several combinations of adjuvants, as follows:

1) 3.0 g. 1,3-diaminopropane, 2.0 g. sodium N-coconut-N-methyl taurate,with no thickener; pH 9.0;

(2) 2.0 g. N-phenyldiethanolamine, 1.5 g. sodium lignosulfonate, and 2.0g. hydroxyethylcellulose; pH 8.0;

(3) 3.0 g. ethanolamine, 1.5 g. sodium lignosulfonate,

and 2.0 g. hydroxyethylcellulose; pH 8.5; and

(4) 0.25 g. triisopropanolamine, 4.0 g. coconut acid ethanolamide, 2.0g. coconut acid diethanolamide, 3.0 g. coco amine crotonic acidcondensate; pH 7.5.

The dyeings were all strong level maroon shades, similar in shade andstrength on both kinds of hair. The dyeings (1) above were particularlyheavy, as compared to (2), (3) and (4) which were all essentially alike.

The same dye was also applied by Procedure B using 0.15 g. dye combinedwith the following:

(1) 2.0 g. octylphenol polyethylene oxide condensate with no thickener,citric acid to pH 5;

(2) 1.0 g. glycerol monostearate, 3.0 g. dodecyl benzyl 38 dimethylammonium chloride; ammonium sulfate added; pH 6.5.

The dyeings were level maroons, similar on both kinds of hair. Dyeings(1) were heavier than dyeings (2), but both were strong.

Example 100 The product of Example 82 was dyed on hair by Procedure A,using 0.15 g. dye and the following combinations of adjuvants:

(l) 3.0 g. diethylenetriamine, 1.0 g. sodium dodecylbenzenesulfonate,2.0 g. hydroxyethylcellulose; pH 9.5;

(2) 4.0 g. isopropanolamine, 3.0 g. nonylphenol polyoxyethylenecondensate, 2.0 g. sodium carboxymethylcellulose; pH 8.5.

The dyeings were a purple shade of very good strength, which were fastto three successive shampooings.

The same dye was applied by Procedure B using 0.15 g. dye, combined withthe following:

(1) 1.5 g. polyoxyethylene monostearate, 2.0 g. hydroxyethylcellulose,lactic acid added to pH 6.5;

(2) 2.0 g. cetyl pyridinium bromide, 1.5 g. polyoxyethylated fattyalcohol, citric acid to pH 7.

The dyeings were in moderately strong purple shades, fast to shampooingand rubbing.

The same dye was also applied by Procedure C and gave moderately strongpurple dyeings. The dye was shown to be completely stable in theperoxide composition, since when it was dyed by Procedure C but withoutperoxide (substituting an equal volume of Water), it gave the same shadeand strength as when dyed with peroxide.

The following additional dyeings, performed according to Procedure A,are listed in Table I, wherein the various columns designate the dye,the alkaline agent, the surfactant, and the thickening agent, togetherwith the amount of each component used, the final pH of the composition,the color produced on gray and bleached hair, and any especiallynoteworthy characteristics of the composition or dyeings.

TABLE I Dye: prodnot of Amount of Example dye, g. Alkaline agentSurfactant Thickening agent pH Color on hair Comments 0.3 5 g.triethylenetetramine.. 0.5 sodium lauryl 2 g. methylcellulose 9.5 Bluishviolet"-..

s a e. 0.5 rlo do do 0. 05 2 g. diethanolamine 1 g. polyethoxylated 1 g.acrylic acid allyl- Fast to 3 nonylphenol. sucrose copolymer. shampoos.0. 25 3 g. N-phenyldiethanol- 4 g. coconut acid (11- 3 g. sodiumcarboxyamine. ethanolamide. methylceliulose. 0.5 rlo do do 0. 1 1 g.1,2-diaminopropane.-- 0.5 g. sodium ligno- None sulionate. 0. 1 1 g.triethy1amine 2 g. laurie diethanol- 2 g. methylcellulose-.:..--- Dyebath stable ami e. on storage. 0. 2 4 g. triethanolamine.-.;-- 3 g.sodium N-oleoyl- 3 g. sodium earboxy- N-methyl taurate. methylcellulose.0.2 --.-.-do 0.5 g. sodium diectyl 2 g. sodium carboxysulfosuccinate.methylcellulose. 0. 3 4 g. 8,3-iminodipropyl 1 g. ethylene glycol 3 g.hydroxyethylamine. monostearate. cellulose. 0.75 do o l do Y 0. 15 2 g.morpholine 3 g. polyethoxylated 3 g. methylcellulose Fast to 3 coconutfatty acid shampoos. amide. 18. 0.2 0.5 g. isopropanolamine 2.5 g. cocoamine crotonic N 7.5 do M acid condensate, 3.0 g. coconut aciddiethanolamide. 0. 1 2 g. ethylenediamine 2.5 g. sodium lauryl 2 g.sodium alginate 8. 5 Orange Dye bath stable I s ate. on storage. 0.1 2g. dlethylelletflamill6. 1.5 g. g1ycerylstearate 2 g. methy1ce1lulose.'8.0 Red Fast to 3 sham 00s. 25 0. 25 3 g. 1,3-diaminopropane--- 2 g.sodium lignosulfonate- 3 g. sodium carboxy- 8. 5 Red p methylcellulose.27 0. 25 3g. tflethylenetetraminm- 3g. nonylphenoxy do 9 0 Purplepo1y(ethyleneoxy)- ethan l. 29 0. 25 2 g. 3,3-imino-dipropyl- 2 g.sodium dodecyl- 3 g. methyleellulose-:.:.;- 8. 5 Red amine.benzenesulfonate. 31 0.25 2 g. triethanolamineflrnn 3g.us1?dt1um1aury1-do.....:--.-.; 9.5 Red s a e. 31 0. -d0 do c do r 9.5 Red 0. 3 3 g.1,3-diaminopropane..- 2.5 g. sodium N-methyl- 3 g. hydroxyethyl- 8. 5Orange N-palmitoyl taurate. eellouse. 0. 25 4 g. triethanolamine 3 g.polyoxyethylene do e 9.5 Red laurie ester. 0.2 3 g. N-phenyldiethanol- 3g. sodium myristyl 2.5 g. sodium carboxy- 9. 5 Vio1et.-.

amine. 5 ate. methyleellulose. 0. 15 2.5 g. N-pheny1diethanol- 3 g.Iaunc diethanol- 2 g. methy1ce]1u1ose 8. 5 Red.-..:-.-:::: Dye bathstable amine. amide. on storage.

